Isopropyl 2, 4-dinitro-6-sec.-butylphenyl carbonate



United States Patent 3,234,260 ISOPROPYL 2,4-DINITRO-6-SEC.-BUTYLPHENYL CARBONATE Max Pianka and Donald John Polton, Hertfordshire, England, assignors to The Murphy Chemical Company Limited, St. Albans, England, a British company No Drawing. Filed Mar. 15, 1962, Ser. No. 180,013 Claims priority, application Great Britain, Mar. 22, 1961, 10,501/ 61 1 Claim. (Cl. 260-463) This invention is concerned with improvements in or relating to pesticides.

We have found that a novel group of organic carbonate esters have marked pesticidal activity, individual esters of the group possessing pesticidal activity in one or more of the following capacities: acaricidal, ovicidal, fungicidal, and insecticidal. Whilst some of the esters appear to possess significant activity against one particular pest, others possess activity against two or more pests. For example, some of the esters have marked acaricidal and ovicidal activity, whilst others are active against two diiferent fungi. It will be appreciated that this dual activity is highly important in agriculture and horticulture.

Since the compounds according to the invention are.

in which:

X and Y are the same or dilferent and each is an oxygen or a sulphur atom;

R is a saturated or unsaturated aliphatic hydrocaron residue which may be substituted with one or more of the following substituents:

halogen atoms, amino groups, substituted amino groups, salted amino groups, hydroxyl groups, aryl groups, acyl groups, alkoxy groups, alkylthio groups, alicyclic and heterocyclic groups; or is a phenyl, chlorophenyl, nitrophenyl, naphthyl, tolyl, heterocyclic or alicyclic group; one of the groups R and R" is a nitro group and the other is an aliphatic hydocarbon group having at least three carbon atoms, a phenyl, substituted phenyl, cyclohexyl or substituted cyclohexyl group.

R may, for example, be an alkyl group containing 1-18 carbon atoms, preferably 1-12 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, decyl etc,

3,234,260 Patented Feb. 8, 1966 "ice R may however be an unsaturated aliphatic group e.g. an allyl or substituted allyl group.

As stated above X and Y may be the same or ditferent and each represents an oxygen or sulphur atom. In general, the carbonates (X=Y=O), thionothiolocarbonates (X=Yfl) or thiolocarbonates (X=O; Y'--S) are preferred due to their generally better pesticidal activity.

Where R or R" is other than a nitro group this may, for example, be a branched aliphatic hydrocarbon group containing 3-12 carbon atoms. It is preferred that the group R" be a nitro group.

Compounds according to the invention which are especially valuable in view of their important pesticidal activity are those having the formula:

1 \*Oa (II) where R, X and Y have the meanings defined above and 1 R' is a branched alkyl group containing 3-8, preferably 4-8, carbon atoms.

Particularly useful compounds of Formula II are those in which R' represents a sec.-butyl group straight or branched chain alkyl group containing from 1 to 8 carbon atoms or is a tetrahydro-furfuryl group,

were found to be especially useful, many of them having good multi-pesticidal activity.

Particularly preferred individual compounds according to the invention on account of their outstanding pesticidal activity are the following:

(a) lsopropyl 2,4-dinitro-6-sec.-butylphenyl carbonate 0H (|).C0.0-GH

This compound has very good acaricidal activity and has given kills of of spiders resistant to organophosphorus compounds at concentrations as low as 0.001%. It also shows good activity against cucumber powdery mildew, apple mildew and diamond backed caterpillar. This wide range of pesticidal activity makes the compound very important for many horticultural 5 purposes.

(b) 1'-methylheptyl 2,4-dinitro-6-sec.-butylphenyl (d) 3-(and 2-) methylbutyl 2,4-dinitr0-6-sec.-butyl phenyl carbonate r (|)-'OO-OCH2CH2CH-CH2 40 CgH5-'CH 02 I NO:

and

:(ilH; (*).CO.OCH:.OH.OzH5

open-(13H N01 CH3 I I NO:

These compounds are outstandingly active against greenhouse red spider and have given kills of 98% at concentration of only 0.001%. They also show good ac- .tivity against apple mildew.

(e) a-Tetra'hydro-furfuryl 2,4-dinitro-6-sec.-butylphenyl carbonate O.C O.O-CH2 I This compound is also -very active against greenhousered spider and has given l 00% kills at concentrations as low as 0.0005%. It also shows very good activity against both cucumber powdery mildew and apple mildew.

(f) Very similar properties are shown by methyl 2,4- dinitro-6-sec.-butylphenyl thiolocarbonate (g) Methyl 2,4-dinitro-6-tert.-butylphenyl carbonate O.C0.0CH3 C 3 l This compound has good activity against greenhouse red spider combined with marked ovicidal activity.

(h) Ethyl 2,4-dinitro-6-tert.-butylphenyl carbonate 0.00.0.01H: C33 l CH3C NO2 I NO;

This compound has acaricidal and ovicidal activity (similar to that of the corresponding methyl compound described above) and also possess marked activity against both cucumber powdery mildew and apple mildew.

(i) rt-Hexyl 2,4-dinitr0-6-tert.-butylphenyl carbonate O.C0.0.CsH1:

Cg: l CHa-G -NO2 This com-pound is distinguished by good acaricidal activity.

(j) Methyl 2,4-dinitro-6-(1'-methylbutyl)-phenyl carbonate (I).CO.OCH:4

CsHz-CH- l lo: This compound has a goodactivity against greenhouse red spider as well as good activity both against cucumber powdery mildew and apple mildew.

(k) lsopropyl 2,4-dinitro-6-(1'-methylbutyl)-phenyl carbonate CH; 0.0 0.0 OH I CH3 CgYi -OH- -NO1 This compound has good activityagainst greenhouse.

5 red spider and also possesses ovicidal activity as well as marked activity against powdery mildew.

(l) 3'-(and 2'-)methylbzltyl 2,4-dinitro-6-(1"-methylbutyl)-phenyl carbonate (i).CO.OCH2(']H.CzHa

l NO: These compounds combine very good activity against greenhouse red spider with good activity against apple mildew.

(m) Ethyl 2,4-dinitr-6-(1'-methylheptyl)-phenyl carbonate O-C O OCgH (n) Methyl2,4-cli1zitr0-6-(1-methyllzeptyl)-phenyl carbonate O.C0.0.CH:

l NO:

Both compounds (m) and (It) show a wide range of activity, being active against greenhouse red spider, cucumber powdery mildew, apple mildew, rose mildew and apple scab (Venturia z'naequalis) Their combined activity against apple mildew and apple scab is of particular importance.

(o) M ethyl 2,4-dim'ir06-(1 '-methy Uzeptyl) -phenyl thiorzothiolo-carb onate 10. C 8.8 C Ha This compound showed good activity against greenhouse red spider and cucumber powdery mildew.

(p) Methyl 2,4-dinitro-6-(1'-methylheptyl)-phenyl thiolo carbonate (|).CO.S.CHs

C H oH NO1 This compound showed good activity against apple mildew and apple scab and also showed excellent eradicant properties towards these fungi. This dual activity is, of

course, extremely important in practical application.

Compounds of the formulae were found to possess excellent activity against spider mites resistant to organophosphorus compounds such as parathion (O, O-diethyl O-p-nitrophenyl phosphorothioate) and schradan (octamethylpyrophosphoramide). Moreover many compounds of these general formulae also exhibit aphicidal activity against caterpillar.

The compounds according to the invention may be prepared in any desired way. In one convenient method of preparation of compounds of general Formula I, the corresponding phenol:

it" (IV) where R and R have the meanings defined above, may be reacted with a haloformic acid ester of the formula:

Z.CX.YR

where X, Y and R have the meanings defined above, and Z is chlorine, bromine or iodine, preferably chlorine. The reaction is preferably conducted in the presence of an acid binding agent, e.g. a tertiary base such as pyridine o-r dimethylaniline. The reaction is conveniently effected in the presence of an inert solvent such as diethyl ether, benzene or tetrahydrofuran.

The compounds according to the invention may also be prepared by reaction of a phenoxide of the formula:

n (VI) (where R and R" have the meanings defined above and M represents an alkali metal, preferably sodium or potassium) with a haloformic ester of the formula:

Z.CV.Y.R (V) (where X, Y, R and Z have the meanings defined above) in solution in an inert organic solvent.

Particularly suitable solvents for this reaction are ketones, e.g. acetone.

The p'henoxide of Formula VI may be preformed or, preferably, may be formed in situ in the inert organic solvent prior to introduction of the haloformic acid ester by reaction of the parent phenol with a suitable alkali metal compound, e.g. the hydroxide, carbonate or bicarbonate.

The preparation of the compounds according to the invention by the reaction of a phenoxide of general Formula V1 with a compound of general Formula V is particularly advantageous since the use of the phenoxide in place of the parent phenol (IV) and a tertiary base leads, in general, to improve yields being obtained.

However, another advantageous method of preparing the compounds according to the invention comprises the simultaneous reaction of the parent phenol (IV) with a haloformic acid ester (V) in an inert organic solvent (e.g. a ketone such as acetone) in the presence of an alkali metal carbonate or alkali metal bicarbonate, preferably an alkali metal carbonate. By using this method, it is also possible to obtain improved yields as compared with the use of theparent phenol (IV) and a tertiary base. It is to be observed that alkali metal hydroxides cannot be used in place of alkali metal carbonate or alkali metal bicarbonate since these will decompose the haloformic acid ester.

The haloformic acid esters (V) may conveniently be prepared by reaction of a compound of the formula RYH with a compound of the formula CXZ according to the equation:

Thus, the preferred chloroformic acid esters maybe jproduced by the following reactions:

In general, these reactions may be carried out in the presence of aluminum chloride as catalyst and where required in the presence of an acid binding agent.

The new compounds according to the invention can be formulated for use in any desired way. Generally such formulations will include the compound in association with a suitable carrier or diluent. Such carriers may be liquid or solid and designed to aid the application of the com-pound either by way of dispersing it where it is to be applied or to provide a formulation which can be made by the user into a dispersible preparation.

Liquid preparations thus include preparations of the compound in the form of solutions or emulsions which can be used on their own or be adapted to be made up with water or other diluents to form sprays etc.; insuch cases the carrier is a solvent or emulsion base non-phytotoxic under the conditions of use. Generally such preparations will include a wetting, dispersing or emulsifying agent. Other liquid preparations include aerosols in which the compound is associated with a liquid carrier or propellant.

Solid preparations include dusts and wettable powders, granulates and pellets, and semi-solid preparations such as pastes. Such preparations may include inert solid or liquid diluents such as clays, which may themselves have wetting properties, and/or wetting, dispersing or emulsifying agents; binding and/or adhesive agents may also be included. Solid preparations also include thermal fumigating mixtures wherein the compound is associated with a solid pyrotechnic component.

For the better understanding of the invention, the following examples are given by way of illustration only. In these examples temperatures are given in degrees centi- Test for activity against Erysiphe cichoracearum The wettable powder was diluted with water to obtain the required concentration of the toxicant. Cucumber plants were sprayed with this dilution and placed in a greenhouse under artifiicial illumination. Spores of cucumber mildew were blown on to the plants. Another spraying was carried out after 10 days and the incidence of infection assessed at the end of the treatment. Where a dust is indicated in the tables, the cucumber plants were dusted with a dust prepared by mixing 5 parts of the toxicant with parts of china clay instead of being sprayed with the wettable powder. Otherwise the technique of infection and the assessment of the incidence of the infection after treatment were the same.

Test for activity against Podosphaera leuootricha The wettable powder was diluted with water to the required concentration of the toxicant. Apple rootstocks placed in a greenhouse under artificial illumination were sprayed with this dilution. Spores of apple mildew were blown on to the rootstocks. Two further applications at 10-day intervals were made and the incidence of infection was assessed at the end of the treatment.

Test for activity against Venturia inaequalis The formulated toxicant was diluted with water to obtain the required concentration of the toxicant. Apple rootstocks were sprayed under artificial illumination with this mixture. After several hours the deposit had dried. On the same day the rootstocks were placed in an infection chamber and the upper surfaces of the leaves were sprayed with a suspension containing approx. 500,000

spores of Ventaria inaequalis per cc. After 48 hours the rootstocks were removed from the infection chamber and placed in a greenhouse under artificial illumination. The lnfection incidence was then assessed after 21 days.

EXAMPLE 1 Isopropyl 2,4-dinitro-6-sec.-butylp henyl carbonate The basic equations underlying the preparation of this compound are:

2,4-dinitro-6-sec.-butylphenol (96.6% pure, 49.7 g.) was dissolved with stirring in acetone (400 cc.). To the solution was added potassium hydroxide (11.2 g.) and the mixture stirred till all reactants were in solution. To this solution was added, all at once, a solution of isopropyl chloroformate (96% pure, 25.3 g.) in acetone (100 cc.). The mixture was refluxed for 2 hours. After cooling, the precipitated potassium chloride was filtered off, washed with a little acetone, dried and weighed. Weight of potassium chloride was 14.5 g. (98% of theoretical). The acetone was then stripped off. To the residue (71.2 g.) was added methanol (100 cc.) and the solution stirred. crystallisation started immediately and continued overnight. The crystalline solid was filtered oif and washed on the filter with very little methanol to give almost colourless washings. The white crystalline solid (first crop) weighed 46.6 g. (71.5% of theoretical), M.P. 55-57. The mother liquor (without the washings) was kept overnight at -9. The second crop of a white crystalline solid was filtered oif weighing 7.8 g. (12% of theoretical), M.P. 5457. On recrystallisation from petrol, B.P. 40-60", almost white crystals, melting at 56-57, were obtained. (Found: N, 8.46. C H N O requires N, 8.59%.)

Total yield of isopropyl 2,4-dinitro-6-sec.-butylphenyl carbonate was therefore 54.4 g. (83.5% of theoretical).

By repeating this method but using sodium carbonate or potassium carbonate instead of potassium hydroxide, isopropyl 2,4-dinitro-sec.-butylphenyl carbonate was obtained in 81% yield and 91% yield respectively.

This compound has exceptionally good acaricidal activity coupled with safety to living plants, and has a very favourable mammalian toxicity: acute oral LD to male mice is greater than 1500 mg./kg., acute oral LD to male rats is about 400 mg./kg. body weight.

The compound was formulated as follows: parts of the compound were mixed with 20 parts of Lissapol NX (a polyethylene glycol ether) and made up to =100 parts by volume with acetone. This solution was diluted with water to contain 0.001% of the compound. Dwarf bean plants were infested with 50 resistant greenhouse red spiders per plant. The plants were dipped in the diluted solution and observations were made after 48 hours, when it was found that all the spiders were dead. In parallel tests schradan (octamethylpyrophosphoramide) and parathion (0,0-diethyl O-p-nitrophenyl phosphorothioate) at concentrations of 0.05% of toxicant gave only 20% and 30% kills of this resistant spider respectively.

The compound was also formulated as a 50% wettable powder as follows: a mixture of 50 parts of the toxicant, 7 parts of finely divided synthetic calcium silicate, 6 parts of powdered calcium salt of sulphite cellulose waste liquor, 05 part of 80% sodium lauryl sulphate and 38.5 parts of china clay having a state of subdivision such that at least 95% thereof passes through a 300 mesh B.S.S. sieve, was intimately mixed and ground. When required for use the powder was mixed with water to give the desired concentration. When diluted to 0.001% of the toxicant and sprayed on bean plants infested with resistant greenhouse red spider it gave a complete kill of spider after 48 hours.

The compound was also effective against Plutella maculzpennis giving a complete kill of the second and third instar at a concentration of 0.05% of toxicant.

The compound gave complete protection against cucumber powdery mildew (Er ysiphe cichoracearum) at a concentration of 0.05% of the toxicant and against apple mildew (Potiosphnera leucotricha), with no phytotoxicity to the foliage or fruit.

A conventional thermal fumigating device was prepared containing 30% by weight of the toxicant in admixture with potassium chlorate, lactose and china clay. The quantity of toxicant was calculated so that, on ignition, it yielded 1 g. of toxicant in 1000 cubic feet of space. Cucumber plants infested with resistant greenhouse red 10 spider were placed in a cubicle and the device ignited. Observations after 48 hours were made when it was found that all the spider was killed.

An aerosol was prepared in which the toxicant was dissolved in acetone to give a 10% w./v. solution. This was dispersed with the aid of compressed air to yield 1 g. of toxicant per 1000 cubic feet. This was applied to cucumber plants infested with resistant greenhouse red spiders. After 48 hours it was found that all the spiders were killed. No phytotoxicity to the plants was observed from these treatments. I

The product was also formulated as an emulsifiable concentrate as follows: 3 lbs. of the toxicant were mixed with 0.75 lb. of a blend of an aryl alkyl sulphonate, an alkyl aryl polyethylene oxide ether and an alkyl polyethylene oxide ether and made up to 1 gallon with coal tar naphtha, of which boils below 190. This gave similar aca-ricidal and fungicidal results to those given by the wettable powder.

EXAMPLE 2 1-methylheptyl-Z,4-dinitro-6-sec.-butylphenyl carbonate To a solution of 2,4-dinitro-6-sec.-butylphenol (60 g.) dissolved in ether (500 cc.) was added pyridine (20 g.) and then, while cooling and stirring, a solution of octan- 2-yl chloroformate (48 g.) in ether cc.). Pyridine hydrochloride precipitated immediately and was filtered oil? and the ethereal solution washed with dilute hydrochloric acid, then with water. The ethereal solution was then dried over anhydrous sodium sulphate, filtered, and the ether removed leaving a clear brownish oil, weighing 98 g. (theory requires 99 g.). It had a refractive index r2 1.5021. (Found: N, 7.05. C H N O requires N, 7.07%.)

This oil was formulated as a 25% wettable powder as follows: 25 parts of the oil, 15 parts of a polyoxyethylene oleate, 20 parts of finely divided synthetic calcium silicate and 40 parts of finely divided china clay (as described in Example 1) were mixed and ground. When diluted to 0.01% and applied to resistant greenhouse red spider on dwarf beans it gave complete kill of the spider. Moreover this compound was effective against fruit tree red spider (Panonychus ulmi) giving a complete kill of spider adults when fruit trees in orchards were sprayed with this wettable powder at a concentration of 0.025% of the toxicant. It caused no damage to foliage or fruit.

Using the general method of Example 2, further compounds of the general Formula VII below were prepared by reaction of the corresponding phenol with the appropriate chloroformic acid ester.

OCJCYR For the sake of convenience the nature of the products, their characteristics and yields obtained, together with biological results are shown in Table I.

The abbreviation W.P. indicates wettable powder which, in the case of the 12.5% W.P. was prepared as follows: 12.5 parts of the compound, 0.25 part of 80% sodium lauryl sulphate, 6 parts of powdered calcium salt of sulphite cellulose waste liquor, and 81.25 parts of fine china clay (described in Example 1) were intimately mixed and ground. The other W.P.s were prepared in like manner.

In order to prepare a 5% miscible preparation 5 parts of the compounds were mixed with 10 parts of Lissapol NX and made up to 100 parts by volume with acetone or another suitable solvent. Other miscible preparations are made using a similar procedure.

TABLE I Resistant green- Erysiphe cz'chora- Podosphaera Zeucohouse red spider ceamm tricha Ex, Yield Formula- No. X Y R M.P., 0. m percent tion Cnc., Kill, Cone, Proteo Cone, Protecpercent percent percent tion, percent tlon,

percent percent WI. 0 91. 5% mls- 0. 001 99 cible. O 91.5 do 0.005 97 O 0.005 98 O 0.01 100 0.05 100 O n-C Hn 1. 5031 0. 005 97 O n-CmHzn 0. 01 100 O CH(CH3)C3H1 1 46-48 0.005 100 0.05 98 0.05 99 O OH(CH3)C;H5 1. 5153 0.001 100 0.05 99 0.05 100 GHZCH2CH(CH3)CH3, 85%- o {CHZCH(CH3) CHZCHS, 1 5100 0. 001 08 o. 05 100 O CHzCH2CH(CHs) OHzC(CHa)a 1. 5093 0.01 99 O CHZCHQC] 3 77-79 0.005 99 O CHzCHgOCzHn 4 52-53 0.005 100 0 CH2CHZCHI 1. 5330 0.001 93 0 CHgCHBf-CHzBI 1. 5651 0. 005 100 S S a 85-86 0. 01 S S 1. 5954 0.05 s Q 1. 5571 0. 001

1 From methanol. 2 Low melting solid. 3 From di-lsopropyl ether. 1 From petrol, B.P., -40.

Using the general method of Example 1 further com- EXAMPLE 29 pounds of the general Formula VII above were prepared by reaction of potassium phenoxide of the formula p-Nl rophenyl 2,4-dimtr0-6-sec.-butylphen l carbonate This compound was prepared from p-nitrophenyl chlo- OK roformate and 2,4-dinitro-6-sec.-butylphenol according to I the method described in Example 2, but using dimethylaniline instead of pyridine. p-Nitrophenyl 2,4-dinitro-6- sec.-butylphenyl carbonate was obtained as a dark brown oil, n 1.571, in 99% yield. It was formulated as a 5% miscible and gave 99% kill of resistant greenhouse N02 red spider at a concentration of 0.005% of the toxicant.

EXAMPLE 30 with the appropriate chloroformic acid ester.

When the final product was found to be contaminated Z-mercaptobenzthiazolyl 2,4-dinitr0-6-sec.-butylphenyl with unreacted 2,4-dinitro-6-sec.-butylphenol, the product arbo t was dissolved in benzene and stirred for several hours with excess powdered potassium hydroxide or anhydrous This compound was prepared from Z-mercaptobenzotassium carbonate, The benzene solution was then thiazolyl chloroforrnate and 2,4-din1tro-6-sec.-butylphenol filtered from the solid consisting of excess of potassium using the method described in Example 29. The desired hydroxide M ta iu arbonate and otassium 2,4- compound was obtained as a solid melting at 163-l65 'dinitro-6-sec.-butylphenoxide and the benzene removed after recrystallisation from ethyl acetate. (N as nitrofrom the filtrate under reduced pressure. groups--Found: N, 6.3; required N, 6.5%.) It was TABLE II Resistant green- Erysz'phe Podosphaera house red spider cichoracearum leucotricha Example Yield,

0 1 ti X Y R MI" 0. percent Formula on Conc., Kill, Cone, Protec- Cone, Protecpercent percent percent on, percent tlon,

percent percent 39-41 93 12.5 W.P 0. 0005 0.05 as 0.05 100 11111: 8 g 02455 78 25% ivv.1 0. 0005 100 0. 05 09 0. 05 100 1 From petrol, HR, 40-60".

:13 formulated as a 12.5% wettable powder and it gave 87% kill of resistant greenhouse red spider at a concentration of 0.01% of the toxicant.

EXAMPLE 3 l N,N-diethylaminoethyl 2,4-dinitro-6-tert.-butylphenyl carbonate To a solution of phosgene in ether (20% w./v.; 20 cc.) was added a. solution of diethylarninoethanol (3.9 g.) in ether (10 cc.), while stirring, at about 0' C. The solid that precipitated was washed with ether by decantation and to a suspension of this solid in ether was added a solution of potassium 2,4-dinitro-6-tert.-butyl phenoxide (9.3 g.) in acetone (50 cc.). Stirring was continued for two hours and the mixture filtered from the solid. The filtrate was evaporated to dryness, and the residue recrystallised ,from isopropanol. It was then dissolved in methanol, neutralised to pH 7 with N/ 2 alcoholic potassium hydroxide. Methanol was then evaporated off and the residue'extracted with benzene. The benzene solutionwas filtered off from the soluble solid, the benzene evaporated .off..and ..the remaining residue recrystallised from di-isopropyl ether. 120421 were obtained.

Pale yellow needles, M.P.

14 EXAMPLE 32 fl-ethylthioethyl 2,4-dinitr0-6-sea-bulyIphenyl carbonate This compound was prepared by reacting potassium 2,4-dinitro-6-sec.-butyl phenoxide and ,B-ethylthioethyl chlorotormate in acetone. The precipitated potassium chloride was filtered oif, acetone was removed from the filtrate, and the residue extracted with benzene. After filtration the benzene was removed from the filtrate leaving a yellow-brown oil (42% of theory), n 1.5441.

Using the general method of Example 1 the following compounds of the general Formula VIII O.CX.YR 2 1 CHr-C- N01 (VIII) were prepared from 2,4-dinitro-6-tert.-butylphenol, potassium hydroxide and the appropriate chloroformate. \Vhere necessary the reaction mixtures were refluxed until the reaction was complete and no more potassium chloride precipitated.

TABLE III Resistant green- Erysiphc Podosphaera house red spider cichomcearum leucotricha Example Yield,

No. X Y R M.P.,C. percent Formulation A Cone, Kill, Cone, Protec- Cone, Protecpercent percent percent tion, percent tion,

percent percent 0 CH 0.005 98 0 8 0.1L 0.005 100 0.05 04 0.05 05 o o 1 o %q 859 49-51 0-0005 97 2 2 3 2 o O{ -i 00-01 01 2a%w.P 0.0005 100 0.05 100 0.05 100 0 O CHgCH=CH2 52-55 5% miscible. 0.005 100 1 From petrol (13.1. -60). 3 From petrol (B.P., -80).

3 From methanol.

50 the appropriate chloroformate.

4 From aqueous methanol.

Using the general method of Example 32 the following compounds of the general Formula VIII were prepared from potassium 2,4-dinitr0-6-tert.-butyl phenoxide and TABLE IV Resistant gredenhouse red or Example No. X Y R M.P., 0. Yield, Formulation percent 00110., Kill, percent percent 0 O n-CGHH 1 5051 62 5% miscible 0. 001 98 O O Il-C oH2r 2 44-46 dO. 0. Cl 98 O O OHzCHzCL. 3 74. 5-76 0. 005 100 O O CHzCHzOH 4 162-165 0.001 62 0 O CHzCHzO C2115 a 59-6G 0. 001 98 O O CHgCHgO C 0 C035 6 101-102. 5 0. l 100 o 0 cal- 3 32-83 0. 01 100 O O CH;. CeHiCi 0 90-91 0.01 82 O O p-Tolyl 3 89-91 0.01 98 O O a-Naphthyl 7 154-155 0.01 87 1 From petrol (B.P., 30%0") 5 From methanol.

3 From petrol B.P., 6080 4 From methyl ethyl ketone.

5 From petrol (B.P., 40-60). From di-isopropyl ether. From petrol (B.P., 160).

3,234,260 7 16 Using the general method of Example 2 the following Products of Example 58 (methyl 2,4-dinitro-6-sec.- compounds of the general Formula VIII were prepared amylphenyl carbonate) and of Example (wnaphthyl from 2,4-dinitro-6-tert.-butylphenol and the appropriate 2,4-dinitro-6-sec.-arnylphenyl carbonate) gave also chloroforrnate, but using benzene as the solvent of kill of the spores of Vemfuria inaequalis (apple scab) at reaction. 5 a concentration of toxicant of 0.006%.

TABLE V Resistant green- Podosphae'ra house red spider lmcotricha Example Yield,

No. X Y R M.P., C. '12,, percent Formulation Conc., Kill, 00110., Protecpercent percent percent tion,per-

cent

48 O O n-C H1 40. 541. 5 0.001 99 49 O O n-C HH 0. 01 50 O O CH(CH3)z 120*122 0.005 73 51 O O CH(OH )CH 87-88 0.01 93 52 O O CH(CH3)GBHI3-- 1.5103 0.01 84 53 O O CHgCHBrCHg'BI'- 86. 5-88. 5 0.01 84 54 O 0 a-Tetrahydro-iurfuryl 66-68 0.01 70 55 O O Oyclohexyl -117 0.01 43 56 O S CH3-.- 127-128 0. 01 93 57 S S OH; a 142-144 0. 01 73 1 From methanol. 1 Low melting solid. 3 From di-isopropyl ether. 4 From petrol, B.P., 40-60".

compounds of the general Formula 1X 30 Using the general method of Example 2 the following compounds of the general Formula X O.C.X.YR

l OC.X.YR O3H7.CH- -N0,

(1X) CaH13CH -N0. CH: 1 (X) I NO:

Using the general method of Example 2, the following were obtained from 2,4-dinitro-6-sec.-amylphenol and the were obtained from 2-(l-methyl-n-heptyl)-4,6-dinitroappropriate chloroformate. phenol and the appropriate chloroformate.

TABLE VI Resistant green- Erysiphe cichora- Podosphaemleuco house red spider cearum tricha Ex. X Y R M.P., C. D20 Yield Formulapercent tion Cone, Kill, 00110., Protec- 00110., Protecpercent percent percent tion, percent tion,

percent percent 0 79 0.001 100 0 05 99 O 89 0.001 100 0.05 99 0 05 100 O 92 o. 01 94 88 0.01 8 100 O. 01 O 98 0.001 O 100 0. 001

O CH CH 00 H 1. 5250 81 0. 001 100 0 O5 100 0 01120520505. 1. 5320 as 0.001 100 O CH 0 H 1. 5589 69 0. 01 O a-Tietr ahydro-furfuryl 1.5350 91 0.01 0 c n. 1.5630 9s 0. 01 O p-Ohlorophenyl 16 0.01 O a-Naphtlngl. 81g C h 8 52 exy 1. 5620 87 d0 0.01 96 1 From petrol, B,P.., 3040". 1 From methanol. 3 From di-lsopropyl ether.

TABLE VII Resistant greon- Ert aiphe Podosphaera Sphaerotheca house red spider cichomceamm Zeucotncha pannosa Example Yield,

N o. X Y R 11,, percent Formulation Cone, Kill, Cone, Protec- Cone, Protec- Cone, Protecpercent percent percent tion, percent tion, percent tion, percent percent percent.

78* O O 1. 522 100 0.01 77 0. 0125 100 0. 0003 100 0. 0125 99 79 O O 1. 513 92. 0.01 83 0. 0125 100 0. 0063 100 0. 0125 100 80 O O 1. 505 93. 5 0. 1 95 0. 0125 100 81 O O CH(CH:)CH 1. 492 90. 5 W.P 0. 0063 100 82 O O CH(CH;) C@H 3 l. 502 96 12.5% W.P- 0. 0063 98 83 O O a-Tetrahydro- 1. 514 94 5% miscible. 0. 001 76 iurfuryl. g 84 S S CH3 1. 563 93. 8 W.P 0. 0125 100 The compounds of these examples also gave virtually 100% control of Vmturz'a inaequclis when applied as a 12.5% W.P. at a concentration of 0. 0125% of toxicant to rootstocks infected with Venturia inaegualis.

EXAMPLE 85 Methyl 2,4-dim'tr0-6-( l' -methylheptyl) -phenyl thz'olocarbonaze To a solution of 2,4-dinitro-6-sec.-octylphenol (6.6 g.; 90% pure) in acetone (40 cc.) potassium hydroxide (1.13 g.) was added. This mixture was stirred at room temperature until a complete solution was obtained. To it a solution of methyl thiolo-chloroformate (2.2 g.) in acetone (10 cc.) was added all at once, the mixture heated under reflux for minutes and allowed to stand for 16 hours at room temperature. The precipitated potassium chloride was filtered 03 (1.29 g.; 94.5% of theory) and the acetone removed from the filtrate under reduced pressure. A brown oil, 11 1.534, weighing 9.9 g., was obtained.

When applied to cucumber mildew (Erysiphe cichoracearum) as a 12.5% W.P. (wettable powder) at a concentration of 0.00625% of toxicant, it gave 98% protection. When applied as a 12.5% Wettable powder at a concentration of 0.025 of toxicant to rootstocks infected with Venturia inaequalis itgave 94% control.

This dual activity is most important in practice. In addition the product had excellent eradicant properties against these fungal infections.

EXAMPLE 86 Ethyl 2,4-dinitro-6-cycl0hexylphenyl carbonate To a solution of 2,4-dinitro--cyclohexylphenol (5.65 g.) and pyridine (1.6 g.) in ether (200 cc.) ethyl chloroformate (2.15 g.) was added with stirring. The precipitated pyridine hydrochloride was filtered after 30 minutes and the ether evaporated off from the filtrate. The residue was recrystallised from petrol (B.P. 40-60") yielding pale yellow prisms, M.P. 76, of ethyl 2,4-dinitro- 6-cyclohexylphenyl carbonate (3.9 g.). (Found: N, 8.1. G i-1 N 0 requires N, 8.3

This was formulated as follows: 10 parts of the toxicant were mixed with 15 parts of Lissapol NX and made up to 100 parts by volume with acetone. 80% kill of resistant greenhouse red spider was obtained at a concentration of 0.01% of the toxicant.

A. 5% dust containing 5 parts of the product and 95 parts of china clay applied to cucumbers gave 99% protection from Erysiphc cichoracearum.

EXAMPLE 87 Methyl 2,4-dinizr0-6-phenylphenyl carbonate To a mixture of 2,4-dinitro-6-phenylphenol (5.2 g.), pyridine (1.63 cc.) and tetrahydrofuran (150 cc.) was EXAMPLE 88 Ethyl 2,4-dinitro-phenylphenyl carbonate The conditions of preparation were as described in Example 87, except that ethyl chloroformate (2.2 g.) was used. Yellow-brown crystals of ethyl 2,4-dinitro-6- phenylphenyl carbonate were obtained from di-isopropyl ether, M.P. 111-113 weighing 4.35 g. (66% of theoretical). (Found: C, 54.6; H, 3.8; N, 8.5. C15I'I12N2O7 requires C, 54.2; H, 3.6; N, 8.4%.)

A kill of 90% of aphids was obtained at a concentration of 0.1% of the toxicant.

EXAMPLE 89 Methyl 2,4-dinitr0-6-phenylphenyl thiolothionocarbonate To a solution of 2,4-dinitro-6-phenylphenol (15.6 g.) and pyridine (4.9 co.) in hot benzene (600 cc.), a solution of methyl thiolothionochloroformate (7.59 g.) in benzene (20 cc.) was added. The mixture was allowed to stand for 24 hours. Water was added to the reaction mixture, the benzene layer separated, dried over anhydrous sodium sulphate, filtered, the benzene removed under reduced pressure from the filtrate and the residue recrystallised from alcohol yielding a crystalline solid melting at 132133 (weight, 6.4 g.). (Found: N, 7.7. C14H1QN205S2 requires N, 8.0%.)

It gave a complete kill of resistant greenhouse red spider at a concentration of 0.01%.

EXAMPLE Ethyl 2,4-dinitr0-6-is0pr0pylphenyl carbonate This compound was prepared as described in Example 2 from 2,4-dinitro-6-isopropylphenol and ethyl chloroformate. The oil that was obtained crystallised on standing. On recrystallisation from petrol (B.P. 30-40) pale 19. yellow prisms were obtained, M.P. 585-59 (60% yield). (Found: N, 9.1. C H N O requires N, 9.4%.)

It' gave a' complete kill of resistant greenhouse red spider at a concentration of 0.01% of toxican t.

EXAMPLE 91 Ethyl 2,6-dinitr-4-terL-butylphenyl carbonate This compound was prepared as described in Example 2 from 2,6-dinitro 4-tert.-butylphenol and ethyl chloroform-ate, using benzene instead of ether as solvent of reaction. On recrystallisation from alcohol a crystalline solidwas obtained, M.P. 7879 (76% yield). (Found: N, 8.9. C H N O requires N, 8.9%.)

It gave 80% kill of resistant greenhouse red spider at 0.005%.

EXAMPLE 92 lsopropyl 2,6-dinitfo-4-tert-butylphenyl carbonate This compound was prepared as in the case of Example 91, but using. isopropyi chloro-formiate. A crystalline solid was obtained, M.P. 97 -98" (89% yield). (Found: N, 8.2'. C 14H19N2O7 re'q'uir'es' N,

EXAMPLE 93 Isopropyl 2,4-dinitr0-6-sea-butylphenyl carbonate 20" infested with resistant greenhouse red spider, in order to demonstrate the ovicidal action of the compounds:

Ovicidal action Compound 01 Example No. Formulation Cone. of toxi- Kill of eggs, cant, percent percent 33 25% W.]? 0. 025 96 0. 01 71 0. 005 63 34 12.5% W? 0. 025 94 0.01 77 0. 005 69 36 25% WP 0.025 9 0. 01 84 0,005 67 48' 25% WP 0. 025 87 I 0. 01 0. 005 52 58'. 25% WP 0.025 94 i 0. 01 87 0.005 84 63 25% WP 0. 025 87 0. 01 0.005 68 We claim: Isopropyl 2,4-dinitro-6-sec.butylphenyl carbonate.

References (Cited by' the Examiner UNITED STATES PATENTS 2,335,237 11/ 1943' Conzetti 260 -463 2,787,631 4/ 1957 Stevens 260-463 2,978,448 4/1961 I-Iassp-acher 2 60463 3,123,522 3'/ 1964 Soherer et ai. 260''463 3,130,037 4/1964 Soherer et a1. 7l2.6'

OTHER REFERENCES Chappell et al.: Ohern. Abstracts, vol. 50 (1956), column 9670 (abstract of Plan-t Disease Reptr. 40 (1956), pages 52-6.

Kixiugawa et al.: J. Pharm. Soc., Japan, vol. 79 (1959), pages 931-3.

Kinugawa et al.: J.- Ph-arm. Soc., Japan, volume 79 (1959), pages 933-7.

NICHOLAS S. RIZZO, Primary Examiner. IRVING MARCUS, Examiner. 

